Synthesis · Controllable proton-conducting pathways: Via situating polyoxometalates in targeting pores of a metal-organic framework

17 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: Main

Route 1: Other

main p.2 · Experimental - Impregnation of HPWs into the larger cages of MIL-101 (1)

Metal precursorsDry MIL-101 (2 g)

Linker precursorsMIL-101 framework

SolventsWater (HPW aqueous solution, 20 mL)

AdditivesHPW (1.0 g in 20 mL water)

AtmosphereAmbient temperature; drying under vacuum

Temperatureambient

Time48

Work-upSolids separated by centrifugation, repeatedly washed with water, and dried under vacuum.

ActivationDry MIL-101 starting material; no separate post-activation stated for product 1.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	dry MIL-101	2 g	main p.2 · Experimental - Impregnation of HPWs into the larger cages of MIL-101 (1)
Additive	H3PW12O40 (HPW)	1.0 g · in 20 mL water	main p.2 · Experimental - Impregnation of HPWs into the larger cages of MIL-101 (1)
Solvent	water	20 mL	main p.2 · Experimental - Impregnation of HPWs into the larger cages of MIL-101 (1)

Complete recipeSource: Main

Route 2: Other

main p.2 · Experimental - Immobilization of HPWs in the smaller cages of MIL-101

Metal precursorsSample 3 (100 mg)

Linker precursorsHPW-loaded MIL-101 framework

SolventsWater (100 mL portions)

AtmosphereAmbient

Temperatureambient

TimeRepeated 1 h soaking cycles

Work-upSolid filtered off after each soak; process repeated until almost no HPW was in filtrate; filtrate monitored by UV-vis.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	100 mg	main p.2 · Experimental - Immobilization of HPWs in the smaller cages of MIL-101
Solvent	water	100 mL per soak	main p.2 · Experimental - Immobilization of HPWs in the smaller cages of MIL-101

Complete recipeSource: Main

Route 3: Other

main p.2 · Experimental - Immobilization of HPWs in the smaller cages of MIL-101

Metal precursorsSample 3 prime (100 mg)

Linker precursorsLower-loading HPW-loaded MIL-101 framework

SolventsWater (100 mL portions)

AtmosphereAmbient

Temperatureambient

TimeRepeated 1 h soaking cycles

Work-upSolid filtered off after each soak; process repeated until almost no HPW was in filtrate; filtrate monitored by UV-vis.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3 prime	100 mg	main p.2 · Experimental - Immobilization of HPWs in the smaller cages of MIL-101
Solvent	water	100 mL per soak	main p.2 · Experimental - Immobilization of HPWs in the smaller cages of MIL-101

Complete recipeSource: Main

Route 4: Hydrothermal

main p.2 · Experimental - Synthesis of MIL-101

Metal precursorsCr(NO3)3.9H2O (2.0 g, 5 mmol)

Linker precursorsTerephthalic acid (0.83 g, 5 mmol)

SolventsDeionized water (20 mL)

AdditivesHPW (2 g, 0.7 mmol); pH adjusted to 3 using 1 M aqueous NaOH

AtmosphereSealed Teflon-lined autoclave; ambient drying

Temperature180

Time20

Work-upSame as MIL-101 route; washed with water and DMF, dried at room temperature.

ActivationDegassed under vacuum at 150 C for 12 h before further treatment.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cr(NO3)3.9H2O	2.0 g, 5 mmol	main p.2 · Experimental - Synthesis of MIL-101
Linker	terephthalic acid	0.83 g, 5 mmol	main p.2 · Experimental - Synthesis of MIL-101
Additive	H3PW12O40 (HPW)	2 g, 0.7 mmol	main p.2 · Experimental - Synthesis of MIL-101
Base	NaOH(aq)	pH adjusted to 3 · 1 M	main p.2 · Experimental - Synthesis of MIL-101
Solvent	deionized water	20 mL	main p.2 · Experimental - Synthesis of MIL-101

Complete recipeSource: Main

Route 5: Hydrothermal

main p.2 · Experimental - Synthesis of MIL-101

Metal precursorsCr(NO3)3.9H2O (2.0 g, 5 mmol)

Linker precursorsTerephthalic acid (0.83 g, 5 mmol)

SolventsDeionized water (20 mL)

AdditivesHPW (1.6 g, 0.6 mmol); pH adjusted to 3 using 1 M aqueous NaOH

AtmosphereSealed Teflon-lined autoclave; ambient drying

Temperature180

Time20

Work-upSame as MIL-101 route; washed with water and DMF, dried at room temperature.

ActivationDegassed under vacuum at 150 C for 12 h before further treatment.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cr(NO3)3.9H2O	2.0 g, 5 mmol	main p.2 · Experimental - Synthesis of MIL-101
Linker	terephthalic acid	0.83 g, 5 mmol	main p.2 · Experimental - Synthesis of MIL-101
Additive	H3PW12O40 (HPW)	1.6 g, 0.6 mmol	main p.2 · Experimental - Synthesis of MIL-101
Base	NaOH(aq)	pH adjusted to 3 · 1 M	main p.2 · Experimental - Synthesis of MIL-101
Solvent	deionized water	20 mL	main p.2 · Experimental - Synthesis of MIL-101

Partial recipeSource: Main

Route 6: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesDiethylenetriamine (2.2 mmol); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upPost-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	diethylenetriamine (DETA)	2.2 mmol	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop	main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Partial recipeSource: Main

Route 7: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesEthylenediamine (2.2 mmol); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upPost-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	ethylenediamine (EN)	2.2 mmol	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop	main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Complete recipeSource: Main

Route 8: Hydrothermal

main p.2 · Experimental - Synthesis of MIL-101

Metal precursorsCr(NO3)3.9H2O (2.0 g, 5 mmol)

Linker precursorsTerephthalic acid (0.83 g, 5 mmol)

SolventsDeionized water (20 mL); washed with distilled water and N,N-dimethylformamide

AtmosphereAmbient atmosphere for drying; sealed Teflon-lined autoclave during heating

Temperature180

Time20

Work-upResulting solid washed with distilled water and DMF and dried at room temperature under ambient atmosphere.

ActivationAs-prepared materials degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cr(NO3)3.9H2O	2.0 g, 5 mmol	main p.2 · Experimental - Synthesis of MIL-101
Linker	terephthalic acid	0.83 g, 5 mmol	main p.2 · Experimental - Synthesis of MIL-101
Solvent	deionized water	20 mL	main p.2 · Experimental - Synthesis of MIL-101
Solvent	N,N-dimethylformamide (DMF)	wash solvent	main p.2 · Experimental - Synthesis of MIL-101

Partial recipeSource: Main

Route 9: Other

main p.2 · Experimental - Synthesis of HPW/TETA (PT)

Metal precursorsNone

Linker precursorsTriethylenetetramine

SolventsWater (20 mL)

AdditivesHPW (1 g, 0.35 mmol); TETA added until precipitation

AtmosphereAmbient

Temperatureambient

Work-upWhite product PT quickly precipitated; further washing/drying not specified in main text.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	H3PW12O40 (HPW)	1 g, 0.35 mmol	main p.2 · Experimental - Synthesis of HPW/TETA (PT)
Additive	triethylenetetramine (TETA)	not specified	main p.2 · Experimental - Synthesis of HPW/TETA (PT)
Solvent	water	20 mL	main p.2 · Experimental - Synthesis of HPW/TETA (PT)

Partial recipeSource: Main

Route 10: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTetraethylenepentamine (2.2 mmol); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upPost-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	tetraethylenepentamine (TEPA)	2.2 mmol	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop	main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Partial recipeSource: Main

Route 11: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTriethylenetetramine (2.2 mmol); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upPost-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	triethylenetetramine (TETA)	2.2 mmol	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop	main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Partial recipeSource: Main

Route 12: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTETA (1.2 mmol); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upSame reaction conditions as TETA@3; post-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	triethylenetetramine (TETA)	1.2 mmol	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop	main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Partial recipeSource: Main

Route 13: Other

main p.6 · Results and discussion · Fig. S17

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTETA (1.7 mmol g^-1); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upSame reaction conditions as TETA@3; post-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.6 · Results and discussion · Fig. S17
Solvent	anhydrous toluene	30 mL	main p.6 · Results and discussion · Fig. S17
Additive	triethylenetetramine (TETA)	1.7 mmol g^-1	main p.6 · Results and discussion · Fig. S17
Acid	concentrated hydrochloric acid	one drop	main p.6 · Results and discussion · Fig. S17

Partial recipeSource: Main

Route 14: Other

main p.6 · Results and discussion · Fig. S17

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTETA (2.7 mmol g^-1); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upSame reaction conditions as TETA@3; post-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.6 · Results and discussion · Fig. S17
Solvent	anhydrous toluene	30 mL	main p.6 · Results and discussion · Fig. S17
Additive	triethylenetetramine (TETA)	2.7 mmol g^-1	main p.6 · Results and discussion · Fig. S17
Acid	concentrated hydrochloric acid	one drop	main p.6 · Results and discussion · Fig. S17

Partial recipeSource: Main

Route 15: Other

main p.6 · Results and discussion · Fig. S17

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTETA (3.2 mmol g^-1); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upSame reaction conditions as TETA@3; post-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.6 · Results and discussion · Fig. S17
Solvent	anhydrous toluene	30 mL	main p.6 · Results and discussion · Fig. S17
Additive	triethylenetetramine (TETA)	3.2 mmol g^-1	main p.6 · Results and discussion · Fig. S17
Acid	concentrated hydrochloric acid	one drop	main p.6 · Results and discussion · Fig. S17

Partial recipeSource: Main

Route 16: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsSample 3 (1.0 g)

Linker precursorsHPW-loaded MIL-101 framework

SolventsAnhydrous toluene (30 mL)

AdditivesTETA (4.2 mmol); one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upSame reaction conditions as TETA@3; post-reflux isolation workup not specified in main text.

ActivationAs-prepared 3 had been degassed under vacuum at 150 C for 12 h before further treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sample 3	1.0 g	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	triethylenetetramine (TETA)	4.2 mmol	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop	main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Partial recipeSource: Main

Route 17: Other

main p.2 · Experimental - Flexible polyamine molecules loading inside 3

Metal precursorsAs-prepared MIL-101

Linker precursorsMIL-101 framework

SolventsAnhydrous toluene (30 mL inferred from same method as TETA@3)

AdditivesTETA; one drop concentrated hydrochloric acid

AtmosphereReflux in anhydrous toluene

Temperaturereflux

Time12

Work-upSame synthetic method as TETA@3 using as-prepared MIL-101 instead of 3.

ActivationActivated MIL-101 at 150 C for 12 h; terminal waters removed.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-prepared MIL-101	not specified	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Solvent	anhydrous toluene	30 mL inferred	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Additive	triethylenetetramine (TETA)	not separately specified	main p.2 · Experimental - Flexible polyamine molecules loading inside 3
Acid	concentrated hydrochloric acid	one drop inferred from same method	main p.2 · Experimental - Flexible polyamine molecules loading inside 3